CN107601549A - The method that nano cuprous oxide is prepared in the simple glycerine of technique and the positive dibutyl ester mixture system of adipic acid - Google Patents
The method that nano cuprous oxide is prepared in the simple glycerine of technique and the positive dibutyl ester mixture system of adipic acid Download PDFInfo
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- CN107601549A CN107601549A CN201710803494.0A CN201710803494A CN107601549A CN 107601549 A CN107601549 A CN 107601549A CN 201710803494 A CN201710803494 A CN 201710803494A CN 107601549 A CN107601549 A CN 107601549A
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- cuprous oxide
- glycerine
- nano cuprous
- temperature
- adipic acid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention discloses the method that nano cuprous oxide is prepared in a kind of simple glycerine of technique and the positive dibutyl ester mixture system of adipic acid, this method is using glycerine and the positive dibutyl ester mixed liquor of adipic acid as reaction system liquid, glycerine reducing agent, copper formate is copper source, the basic sodium sulfonate of cetyl trimethylammonium bromide, dodecane, PVP, lauryl sodium sulfate are dispersant, and the nano cuprous oxide micromeritics of cubic structure has successfully been made using solvent-thermal method.Raw material needed for preparation is cheap and easy to get, technique is simple and convenient to operate, it is reproducible, without waste liquid exclude, met Product Green preparation requirement, these features to carry out industrial scale production be all highly profitable.Nano cuprous oxide material has a wide range of applications in photocatalyst material, industrial chemicals, photoelectron transition material, the negative material of lithium ion battery and ballast material, anti-biotic material etc., has wide market prospects and potential value.
Description
The application is application number：201610800869.3 the applying date：" glycerine and adipic acid are just for 2016-09-05, title
The divisional application of the method that nano cuprous oxide is prepared in dibutyl ester mixture system ".
Technical field
The present invention relates to a kind of method for preparing nano cuprous oxide.
Background technology
Cuprous oxide is a kind of widely used materials of electronic components and industrial chemicals, can be used as the sterilization of agricultural production
Agent, the colouring agent of glass industry production, the catalyst of organic chemical industry's industry, the catalyst that Industry Waste Organic substance in water decomposes.By
In cuprous oxide energy gap 2.2eV, it is a kind of important semi-conducting material, can be used as photoelectron transition material, lithium-ion electric
The negative material and ballast material in pond etc..Therefore preparing specified particle diameter and the Cu2O particles of pattern has broader city
Field prospect and potential value.
The technology of preparing of cuprous oxide common are electrolysis, solid phase method and liquid phase method (sodium sulfite reduction CuSO4 methods,
Hydrazine hydrate reduction method, hydro-thermal method, microwave radiation method, high-energy ray irradiation method, method of glucose reduction) etc..So far, do not send out
Existing glycerine and the positive dibutyl ester of adipic acid make hybrid reaction system liquid, to reduce the side that copper formate prepares nano cuprous oxide powder body
Method and patent document.The preparation method compares that technique is simple, and preparation process no waste discharge is required with the preparation method reported
Raw material sources are extensive and cheap, and product purity is high, and no adhesion, particle diameter is small, has good economic benefit and industrialization
Prospect.
The content of the invention
It is an object of the invention to provide one kind nanometer is prepared in glycerine and the positive dibutyl ester mixture system of adipic acid
Glycerine is both reaction in the positive dibutyl ester mixed liquor reaction system of the method for cuprous oxide crystal grain, particularly glycerine and adipic acid
The important component of system liquid is the simple chemical preparation process of technique of reducing agent again.
The present invention technical solution be：
A kind of method that nano cuprous oxide is prepared in the positive dibutyl ester mixture system of glycerine and adipic acid, it is characterized in that：Bag
Include the following steps：
（1）In a certain amount of glycerine and the positive dibutyl ester mixture system solution of adipic acid, copper formate is added, while add and divide
Powder, stir and suspension is made.
（2）Quickly stirred under normal pressure and heat mixture, when temperature is increased to 350K, control its temperature slowly to raise, often
5 DEG C of temperature controls of rise are observed 30 minutes, finally reaction temperature is strict controlled between 390-410K；
（3）Keep step（2）Reaction temperature, control reaction time 80min-100min, stop heating, be cooled to room temperature, obtain
To the suspension containing nano cuprous oxide；
（4）By step（2）Obtained suspension is filtered under diminished pressure after adding absolute ethyl alcohol or acetone dilution, then with absolute ethyl alcohol or third
Ketone washs repeatedly；
（5）Nano cuprous oxide product vacuum after absolute ethyl alcohol or acetone washing is dried, obtains red nano cuprous oxide
Product.
Step（2）It is continuing with after waste liquid distillation processing after filtering.
Step（1）The volume ratio of the middle positive dibutyl ester of glycerine and adipic acid is 2:1, the mol ratio of glycerine and copper formate is
20:1。
Dispersant is cetyl trimethylammonium bromide, the basic sodium sulfonate of dodecane, PVP or 12
Sodium alkyl sulfate.
The dosage of dispersant is 1/4-the 1/6 of formic acid copper mass.
Step（5）Vacuum drying temperature is 350K, time 480min.
The present invention is that nano cuprous oxide is made in single step reaction in glycerine and the positive dibutyl ester mixture system of adipic acid
Product, it is not necessary to separately add reducing agent, preparation technology is simple, and raw material is easy to get, and cost is relatively low, and obtained nano cuprous oxide is brilliant
For grain size than more uniform, particle diameter is about 10nm -20nm.
Brief description of the drawings
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is the XRD spectrum of nano cuprous oxide crystal grain prepared by embodiment 1.
Fig. 2 is the XRD spectrum of nano cuprous oxide crystal grain prepared by embodiment 2.
Fig. 3 is the XRD spectrum of nano cuprous oxide crystal grain prepared by embodiment 3.
Fig. 4 is the XRD spectrum of nano cuprous oxide crystal grain prepared by embodiment 4.
Embodiment
Embodiment 1
1）60mL glycerine and the positive dibutyl ester mixed liquor (volume ratio 2 of adipic acid::1) it is put into three-necked flask, adds first
Sour copper solid powder 2.50g, while add cetyl trimethylammonium bromide（CTMAB）0.500g, make to mix in the case where being stirred continuously
Compound turns into suspension.
2）The temperature of reactant mixture is slowly raised in quick stirring, when temperature is increased to 390K, control temperature is not
Raise again, continue stirring reaction 80min under temperature control 390K, naturally cool to room temperature, obtain outstanding containing nano cuprous oxide
Turbid.
3）By step 2）Obtained suspension is filtered under diminished pressure after adding 60mL absolute ethyl alcohols or acetone dilution, then with appropriate nothing
Water-ethanol or acetone wash 4 times repeatedly
4）The cuprous oxide powder cleaned up is put into vacuum drying chamber, 480min is dried in vacuo at a temperature of 350K, is obtained
Red nano cuprous oxide powder end crystallite.
Fig. 1 is the XRD spectrum of nano cuprous oxide powder body prepared by the present embodiment 1, and compared with international standard card, it is determined that
That prepared is pure Cu2O products, diffraction maximum from left to right correspond respectively to (110), (111), (200), (220) and (311)
Crystal face, it is the cuprous oxide of cubic structure, does not have miscellaneous peak appearance in figure, illustrate that product nano cuprous oxide purity is higher, according to
Collection of illustrative plates calculates and SEM observations, and the granularity of cuprous oxide is 16nm.
Embodiment 2
1）60mL glycerine and the positive dibutyl ester mixed liquor (volume ratio 2 of adipic acid::1) it is put into three-necked flask, adds formic acid
Copper solid powder 2.50g, while add neopelex（SDBS）0.500g, turn into mixture in the case where being stirred continuously
Suspension.
2）The temperature of reactant mixture is slowly raised in quick stirring, when temperature is increased to 400K, control temperature is not
Raise again, continue stirring reaction 90min under temperature control 400K, naturally cool to room temperature, obtain outstanding containing nano cuprous oxide
Turbid.
3）By step 2）Obtained suspension is filtered under diminished pressure after adding 50mL absolute ethyl alcohols or acetone dilution, then with appropriate nothing
Water-ethanol or acetone wash 3 times repeatedly
4）The cuprous oxide powder cleaned up is put into vacuum drying chamber, 480min is dried in vacuo at a temperature of 350K, is obtained
Red nano cuprous oxide powder end crystal
Fig. 2 is the XRD spectrum of nano cuprous oxide powder body manufactured in the present embodiment, and compared with international standard card, is determined made
That standby is pure Cu2O products, diffraction maximum from left to right correspond respectively to (110), (111), (200), (220) and (311) crystalline substance
Face, it is the cuprous oxide of cubic structure, does not have miscellaneous peak appearance in figure, illustrate that product nano cuprous oxide purity is higher, according to figure
Spectrum calculates and SEM observations, and the granularity of cuprous oxide is 18nm.
Embodiment 3
1）60mL glycerine and the positive dibutyl ester mixed liquor (volume ratio 2 of adipic acid::1) it is put into three-necked flask, adds formic acid
Copper solid powder 2.50g, while add polyvinylpyrrolidone（PVP）0.400g, mixture is set to turn into outstanding in the case where being stirred continuously
Turbid.
2）The temperature of reactant mixture is slowly raised in quick stirring, when temperature is increased to 405K, control temperature is not
Raise again, continue stirring reaction 95min, naturally cool to room temperature, obtain the suspension containing nano cuprous oxide.
3）By step 2）Obtained suspension is filtered under diminished pressure after adding 60mL absolute ethyl alcohols or acetone dilution, then with appropriate nothing
Water-ethanol or acetone wash 4 times repeatedly
4）The cuprous oxide powder cleaned up is put into vacuum drying chamber, 480min is dried in vacuo at a temperature of 350K, is obtained
Red nano cuprous oxide powder end crystal
Fig. 3 is the XRD spectrum of nano cuprous oxide powder body manufactured in the present embodiment, and compared with international standard card, is determined made
That standby is pure Cu2O products, diffraction maximum from left to right correspond respectively to (110), (111), (200), (220) and (311) crystalline substance
Face, it is the cuprous oxide of cubic structure, does not have miscellaneous peak appearance in figure, illustrate that product nano cuprous oxide purity is higher, according to figure
Spectrum calculates and SEM observations, and the granularity of cuprous oxide is 12nm.
Embodiment 4
1）60mL glycerine and the positive dibutyl ester mixed liquor (volume ratio 2 of adipic acid::1) it is put into three-necked flask, adds formic acid
Copper solid powder 2.50g, while add lauryl sodium sulfate（SDS）0.600g, mixture is set to turn into outstanding in the case where being stirred continuously
Turbid.
2）The temperature of reactant mixture is slowly raised in quick stirring, when temperature is increased to 410K, control temperature is not
Raise again, continue stirring reaction 100min, naturally cool to room temperature, obtain the suspension containing nano cuprous oxide.
3）By step 2）Obtained suspension is filtered under diminished pressure after adding 50mL absolute ethyl alcohols or acetone dilution, then with appropriate nothing
Water-ethanol or acetone wash 3 times repeatedly
4）The cuprous oxide powder cleaned up is put into vacuum drying chamber, 480min is dried in vacuo at a temperature of 350K, is obtained
Red nano cuprous oxide powder end crystal
Fig. 4 is the XRD spectrum of nano cuprous oxide powder body manufactured in the present embodiment, and compared with international standard card, is determined made
That standby is pure Cu2O products, diffraction maximum from left to right correspond respectively to (110), (111), (200), (220) and (311) crystalline substance
Face, it is the cuprous oxide of cubic structure, does not have miscellaneous peak appearance in figure, illustrate that product nano cuprous oxide purity is higher, according to figure
Spectrum calculates and SEM observations, and the granularity of cuprous oxide is 20nm.
Claims (1)
1. the method for nano cuprous oxide is prepared in a kind of simple glycerine of technique and the positive dibutyl ester mixture system of adipic acid,
It is characterized in that：Comprise the following steps：
1）60mL glycerine and the positive dibutyl ester mixed liquor (volume ratio 2 of adipic acid:1) it is put into three-necked flask, adds formic acid
Copper solid powder 2.50g, while cetyl trimethylammonium bromide 0.500g is added, mixture is turned into outstanding in the case where being stirred continuously
Turbid；
2）The temperature of reactant mixture is slowly raised in quick stirring, when temperature is increased to 390K, control temperature no longer rises
Height, continue stirring reaction 80min under temperature control 390K, naturally cool to room temperature, obtain the suspension containing nano cuprous oxide；
3）By step 2）Obtained suspension is filtered under diminished pressure after adding 60mL absolute ethyl alcohols or acetone dilution, then with absolute ethyl alcohol or
Acetone washs 4 times repeatedly；
4）The cuprous oxide powder cleaned up is put into vacuum drying chamber, 480min is dried in vacuo at a temperature of 350K, is obtained
Red nano cuprous oxide powder end crystallite；The granularity of cuprous oxide is 16nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710803494.0A CN107601549B (en) | 2016-09-05 | 2016-09-05 | The method of nano cuprous oxide is prepared in the positive dibutyl ester mixture system of the glycerine and adipic acid of simple process |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610800869.3A CN106241854B (en) | 2016-09-05 | 2016-09-05 | The method that nano cuprous oxide is prepared in glycerine and the positive dibutyl ester mixture system of adipic acid |
| CN201710803494.0A CN107601549B (en) | 2016-09-05 | 2016-09-05 | The method of nano cuprous oxide is prepared in the positive dibutyl ester mixture system of the glycerine and adipic acid of simple process |
Related Parent Applications (1)
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| CN201610800869.3A Division CN106241854B (en) | 2016-09-05 | 2016-09-05 | The method that nano cuprous oxide is prepared in glycerine and the positive dibutyl ester mixture system of adipic acid |
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| CN107601549A true CN107601549A (en) | 2018-01-19 |
| CN107601549B CN107601549B (en) | 2019-01-11 |
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| CN201710803494.0A Active CN107601549B (en) | 2016-09-05 | 2016-09-05 | The method of nano cuprous oxide is prepared in the positive dibutyl ester mixture system of the glycerine and adipic acid of simple process |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1894890A1 (en) * | 2005-02-24 | 2008-03-05 | Japan Science and Technology Agency | Transition metal oxide nano-tube |
| CN101157851A (en) * | 2007-08-28 | 2008-04-09 | 华中师范大学 | Preparation method of quantum dot self-assembling nano structural material |
| CN101805011A (en) * | 2010-04-06 | 2010-08-18 | 厦门大学 | Cu2O ultra-fine nano-particles and self-assembly nanospheres as well as preparation method thereof |
| CN102167388A (en) * | 2010-02-26 | 2011-08-31 | 上海亿金纳米科技有限公司 | Novel and large-scale preparation method of nano-cuprous oxide |
| CN102557106A (en) * | 2012-01-12 | 2012-07-11 | 淮阴师范学院 | Preparation method of cuprous oxide hollow nanometer cubes |
| CN103172104A (en) * | 2013-04-03 | 2013-06-26 | 浙江理工大学 | Preparation method of nano cuprous oxide |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101651932B1 (en) * | 2009-10-26 | 2016-08-30 | 한화케미칼 주식회사 | Method for manufacturing of conductive metal thin film using carboxylic acid |
| CN102849778A (en) * | 2012-09-21 | 2013-01-02 | 中国科学院过程工程研究所 | Octahedron cuprous oxide crystal and preparation method thereof |
| CN105883894A (en) * | 2014-12-05 | 2016-08-24 | 天津工业大学 | Preparation method of cuprous oxide mesoporous nanospheres |
-
2016
- 2016-09-05 CN CN201610800869.3A patent/CN106241854B/en not_active Expired - Fee Related
- 2016-09-05 CN CN201710803494.0A patent/CN107601549B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1894890A1 (en) * | 2005-02-24 | 2008-03-05 | Japan Science and Technology Agency | Transition metal oxide nano-tube |
| CN101157851A (en) * | 2007-08-28 | 2008-04-09 | 华中师范大学 | Preparation method of quantum dot self-assembling nano structural material |
| CN102167388A (en) * | 2010-02-26 | 2011-08-31 | 上海亿金纳米科技有限公司 | Novel and large-scale preparation method of nano-cuprous oxide |
| CN101805011A (en) * | 2010-04-06 | 2010-08-18 | 厦门大学 | Cu2O ultra-fine nano-particles and self-assembly nanospheres as well as preparation method thereof |
| CN102557106A (en) * | 2012-01-12 | 2012-07-11 | 淮阴师范学院 | Preparation method of cuprous oxide hollow nanometer cubes |
| CN103172104A (en) * | 2013-04-03 | 2013-06-26 | 浙江理工大学 | Preparation method of nano cuprous oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106241854A (en) | 2016-12-21 |
| CN107601549B (en) | 2019-01-11 |
| CN106241854B (en) | 2017-09-29 |
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Effective date of registration: 20201021 Address after: 226019 No.205, building 6, Nantong University, No.9, Siyuan Road, Nantong City, Jiangsu Province Patentee after: Center for technology transfer, Nantong University Address before: 226019 Jiangsu city of Nantong province sik Road No. 9 Patentee before: NANTONG University |
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